4238-09-9Relevant articles and documents
Alkylation of Nitropyridines via Vicarious Nucleophilic Substitution
Antoniak, Damian,Barbasiewicz, Micha?
supporting information, p. 516 - 519 (2022/01/20)
Electrophilic nitropyridines react with sulfonyl-stabilized carbanions to give products of C-H alkylation via vicarious nucleophilic substitution. The process consists of formation of the Meisenheimer-type adduct followed by base-induced β-elimination of the sulfinic acid (e.g., PhSO2H). Mechanistic studies reveal that in the latter step alkyl substituent and adjacent nitro group tend to planarize for effective stabilization of benzyl anion, and thus, adduct of hindered isopropyl carbanion remains stable toward elimination for steric reasons.
Synthesis of Sulfones and Sulfonyl Derivatives using Sodium (tert-butyldimethylsilyl)oxymethanesulfinate
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Paragraph 0836-0841; 0843; 0845-0846; 0848-0851; 0873-08765, (2021/04/29)
The present invention relates to a method for manufacturing a sulfone and sulfonyl derivative compound using sodium (tert-butyldimethylsilyl)oxymethanesulfinate, which is a novel organic sulfin salt, wherein the novel organic sulfin salt has good stability, environmental friendliness and economy, and is easy to handle, and thus significantly reduces the amount of transition metal catalysts and the amount of organic sulfin salts used when introducing aryl or alkenyl. Also, alkylation, arylation, amination, and fluorination are all possible during secondary functionalization. Therefore, the present invention can be usefully used in preparation and mass production of various kinds of sulfones and derivatives thereof including asymmetric sulfone derivatives.
Silyloxymethanesulfinate as a sulfoxylate equivalent for the modular synthesis of sulfones and sulfonyl derivatives
Kim, Dae-Kwon,Um, Hyun-Suk,Park, Hoyoon,Kim, Seonwoo,Choi, Jin,Lee, Chulbom
, p. 13071 - 13078 (2021/01/09)
An efficient protocol for the modular synthesis of sulfones and sulfonyl derivatives has been developed utilizing sodium tert-butyldimethylsilyloxymethanesulfinate (TBSOMS-Na) as a sulfoxylate (SO22-) equivalent. TBSOMS-Na, easily prepared from the commercial reagents Rongalite and TBSCl, serves as a potent nucleophile in S-alkylation and Cu-catalyzed S-arylation reactions with alkyl and aryl electrophiles. The sulfone products thus obtained can undergo the second bond formation at the sulfur center with various electrophiles without a separate unmasking step to afford sulfones and sulfonyl derivatives such as sulfonamides and sulfonyl fluorides.
Cyanide-Mediated Synthesis of Sulfones and Sulfonamides from Vinyl Sulfones
Lee, Ji-Woong,Roy, Tamal
, p. 455 - 458 (2020/03/13)
We report a facile synthesis of sulfones, β-keto sulfones, and sulfonamides from vinyl sulfones via an addition-elimination sequence where in situ generation of nucleophilic sulfinate ion is mediated by cyanide. The use vinyl sulfones renders high selectivity for S -alkylation to produce sulfones in high yields. In the presence of N -bromosuccinimide, primary and secondary amines underwent sulfonamide formation. A preliminary mechanistic study showed the formation of acrylonitrile as an innocent byproduct, without interfering with the desired reaction pathway while generating a sulfinate nucleophile.
Calcium tungstate: A convenient recoverable catalyst for hydrogen peroxide oxidation
Tressler, Caitlin M.,Stonehouse, Peter,Kyler, Keith S.
supporting information, p. 4875 - 4878 (2016/10/06)
Calcium tungstate was found to be an excellent catalyst for large scale "green" oxidations of organic substrates (amines, alkenes, alcohols, sulfides) with hydrogen peroxide. It displays the unusual dual characteristics of producing a soluble pertungstate species, allowing for homogeneous reaction conditions, but then precipitating, unchanged, at the end of the oxidation. These qualities allow for easy catalyst recovery and minimal waste stream generation for large scale application.
A chemoselective oxidation of sulfides to sulfoxides and sulfones using urea-2,2-dihydroperoxypropane as a novel oxidant
Khosravi, Kaveh,Naserifar, Shirin,Asgari, Atefeh
, p. 749 - 756 (2017/02/05)
Background: Sulfoxides and sulfones have been in the center of attention due to their wide range of promises in various approaches. The functional groups presented in these compounds serve as important building blocks in numerous natural, pharmeceutical and agricultural compounds. These deriatives have been prepared through a multitude of routes which were accompanied by several drawbacks. Therefore, there has been an ever-increasing interest to find a new methodology that leads to the production of these compounds via an environmentally benign path bringing about high yields. Recently, gem-dihydroperoxides have attracted much attention due to their oxidizing power and they have been utilized in several oxidation processes. Methods: We carried out a chemoselective oxidation of sulfides to sulfoxides and sulfones on treatment with urea-2,2-dihydroperoxypropane, a solid oxidant composed of equal amounts of 2,2-dihydroperoxypropane and urea, using THF as the solvent under catalyst-free conditions at room temprature. Results: Sulfides possessing a variety of substitutions namely dialkyl, diaryl, ally l and alkyl-aryl were subjected to the optimized reaction conditions and they could successfully afford different amounts of sulfoxides and sulfones depending on the amount of the oxidant utilized. Based on the results, electron-donating groups accelerated the reaction while electron-withdrawing substituents lowered the reactivity. Conclusion: Urea-2,2-dihydroperoxypropane as a solid oxidant which can be stored for several months without any loss in its activity has proved its capability to oxidize sulfides to sulfoxides and sulfones under catalyst-free and mild conditions. This approach is a cost-effective and environmentally benign methodology via which the products have been synthesized in high yields and short reaction times.
One-pot synthesis of aryl sulfones from organometallic reagents and iodonium salts
Margraf, Natalie,Manolikakes, Georg
, p. 2582 - 2600 (2015/03/18)
A transition-metal-free arylation of lithium, magnesium, and zinc sulfinates with diaryliodonium salts is described. The sulfinic acid salts were prepared from the reaction of the corresponding organometallic reagents and sulfur dioxide. Combination of the three single steps (preparation of the organometallic compound, sulfinate formation, and arylation) leads to a one-pot sequence for the synthesis of aryl sulfones from simple starting materials. The chemoselectivity of unsymmetrical diaryliodonium salts has been investigated. Potential and limitations of this method will be discussed.
Cellulose as an efficient support for Mn(salen)Cl: Application for catalytic oxidation of sulfides to sulfoxides
Mohammadinezhad, Arezou,Nasseri, Mohammad Ali,Salimi, Mehri
, p. 39870 - 39874 (2014/12/11)
Supported Mn(salen)Cl was prepared by immobilization of a homogeneous Mn(salen)Cl complex onto cellulose and characterized by FT-IR, TGA and atomic absorption spectroscopy. This heterogeneous catalyst is able to effectively catalyze the oxidation of aromatic sulfides in good yield under mild conditions. The catalytic activity of Mn(salen)Cl and [Mn(salen)Cl-cellulose] in this reaction was investigated. The heterogeneous catalyst showed higher catalytic activity with respect to the neat Mn(salen)Cl complex. The key advantages of this process are cost effectiveness of the catalyst, reusability of the catalyst and easy work-up. This journal is
Highly efficient selective oxidation of sulfides to sulfoxides by montmorillonite-immobilized metalloporphyrins in the presence of molecular oxygen
Zhou, Xian-Tai,Ji, Hong-Bing
, p. 29 - 32 (2014/06/09)
Highly efficient and selective oxidation of sulfides to sulfoxides with dioxygen catalyzed by cationic meso-tetrakis (1-methyl-4-pyridyl) (TM4PyP) metalloporphyrins immobilized into montmorillonite (MT) interlayer was achieved. Manganese (II) porphyrin (MnTM4PyP-MT) presented excellent activity for the oxidation of sulfides under ambient conditions. In the model oxidation, thioanisole was converted completely and the selectivity towards sulfoxide was up to 95%. This catalyst also showed high activity and selectivity for the most sulfides. The catalyst could be reused consecutively five times without significant loss of activity.
Lithium-titanium exchange of tertiary α-sulfonyl carbanions: Synthesis, structure, dynamics and reactivity of bis(1-sulfonylalkyl) titaniums
Hess, Thomas,Raabe, Gerhard,Gais, Hans-Joachim
, p. 7134 - 7147 (2015/03/04)
Lithium-titanium exchange of tertiary α-sulfonyl carbanions with ClTi(OiPr)3 and Cl2Ti(OiPr)2 in diethyl ether gave bis(1-sulfonylalkyl) titaniums and not the corresponding (1-sulfon-ylalkyl) titaniums. X-ray crystal structure analysis of di(iso-propoxy) bis[1-(phenylsulfonyl) cyclobutyl]titanium and di-(isopropoxy) bis[1-(phenylsulfonyl) isopropyl]titanium showed asymmetric distorted octahedral complexes, having hexaco-ordinate Ti atoms, two C-Ti bonds, four Ti-O bonds, and two four-membered Ti-O-S-Cα rings. According to 1H NMR spectroscopy bis(1-sulfonylcycloalkyl) titaniums are non-flux-ional at room temperature. This suggests that chiral bis(1-sulfonylalkyl) titaniums should be configurationally stable. The bis(1-sulfonylalkyl) titaniums are stable at room temperature towards β-H elimination. They selectively add to benzaldehyde in the presence of acetophenone but do not react with methyl iodide. The reaction of tertiary acyclic α-sulfonyl carbanions with ClTi(OiPr)3 in tetrahydrofuran (THF) gives different titanium derivatives with unspecified structures, which not only selectively react with benzaldehyde in the presence of acetophenone but are also alkylated by methyl iodide.
